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The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols
Author(s) -
Daly Steven,
Tia Maurice,
Garcia Gustavo A.,
Nahon Laurent,
Powis Ivan
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201603771
Subject(s) - photoexcitation , circular dichroism , absolute configuration , chirality (physics) , chemistry , enantiomer , asymmetry , molecular dynamics , chemical physics , stereochemistry , computational chemistry , physics , excitation , chiral symmetry , nambu–jona lasinio model , quantum mechanics , quark
A competition between chiral characteristics alternatively attributable to either conformation or to absolute configuration is identified. Circular dichroism associated with photoexcitation of the outer orbital of configurational enantiomers of 1,3‐ and 2,3‐butanediols has been examined with a focus on the large changes in electron chiral asymmetry produced by different molecular conformations. Experimental gas‐phase measurements offer support for the theoretical modeling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudo‐enantiomerism in 1,3‐butanediol generates a chiral response in the frontier electron dynamics that outweighs the influence of the permanent configurational handedness established at the asymmetrically substituted carbon. Induced conformation, and specifically induced conformational chirality, may thus be a dominating factor in chiral molecular recognition in such systems.